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Alkoxide‐Mediated Preparation of Enolates from Silyl Enol Ethers and Enol Acetates − From Discovery to Synthetic Applications
Author(s) -
Cahard Dominique,
Duhamel Pierre
Publication year - 2001
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200103)2001:6<1023::aid-ejoc1023>3.0.co;2-y
Subject(s) - enol , chemistry , silylation , alkoxide , alkylation , organic chemistry , silyl enol ether , polyene , organic synthesis , catalysis , metalation
A novel route to enolates from silyl enol ethers and enol acetates has been studied and optimized. A range of lithium, sodium and, particularly, potassium enolates were quantitatively prepared under very simple conditions. This new methodology involved an alkoxide‐mediated reaction to form enolates, which were subjected to regiospecific alkylation, aldolisation, or Michael reaction. In some cases, only a catalytic amount of alkali metal alkoxides was needed. A new prenylation method, leading to polyene aldehydes belonging to the vitamin A series, has also been described. Finally, a new concept based on retroaldol reaction has been applied to asymmetric synthesis.